CN113620386A - Electrode material, preparation method thereof and application of electrode material in removing chloride ions and sodium ions in water body - Google Patents
Electrode material, preparation method thereof and application of electrode material in removing chloride ions and sodium ions in water body Download PDFInfo
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- CN113620386A CN113620386A CN202110952603.1A CN202110952603A CN113620386A CN 113620386 A CN113620386 A CN 113620386A CN 202110952603 A CN202110952603 A CN 202110952603A CN 113620386 A CN113620386 A CN 113620386A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an electrode material, a preparation method thereof and application thereof in removing chloride ions and sodium ions in a water body. The invention discloses a bismuth-based electrode material with a layered structure, wherein the bismuth-based electrode material is MBi (sodium niobate) occupied by alkali metal and bismuth element3O4X2M is an alkali metal and X is a halogen. The electrode material disclosed by the invention has a layered structure material with the characteristic of electrochemical reversible phase change reaction, and has the anion and cation removal performance on water containing chloride ions and sodium ions based on the reversible phase change reaction due to the co-occupying characteristic of the layered structure, the contained bismuth element and the alkali metal element. The bismuth-based material is used in an electrochemical ion removal systemIn the system, can effectively remove chloride ions and sodium ions in the water source, has higher removal capacity and can be recycled.
Description
Technical Field
The invention relates to the technical field of electrochemical ion removal, in particular to an electrode material, a preparation method thereof and application thereof in removing chloride ions and sodium ions in a water body.
Background
Water is a basic substance on which human beings rely to live, and with the rapid development of Chinese economy, the problems of shortage of fresh water resources and water pollution are gradually highlighted. The method can effectively solve the problems of shortage of fresh water resources and water pollution by removing ions from seawater and sewage through a proper technical method, and accelerate ecological civilization construction in China and improvement of the quality of life of people. The seawater desalination needs to remove sodium ions, chloride ions and the like in the seawater. The halogen ions and metal ions in the water body mainly come from electroplating industry, machining, mining, nonferrous metal smelting and the like, and the halogen ions mainly comprise chloride ions, fluoride ions, bromide ions, iodide ions, hypochlorite ions and the like; the metal ions mainly include chromium ions, cobalt ions, nickel ions, copper ions, zinc ions, arsenic ions, lead ions, cadmium ions, mercury ions, and the like. The current seawater desalination technology (electrodialysis, reverse osmosis, distillation, etc.) and sewage and wastewater treatment technology (adsorption, coprecipitation, biological absorption, etc.) have defects in the aspects of cost, energy consumption, secondary pollution, ion removal diversity, etc.
The electrochemical ion removal technology has the advantages of low energy consumption, high capacity, no secondary pollution of electrons, recyclability and the like, and has good application prospect in the aspects of capacitive and Faraday electrochemical ion removal. However, the electrochemical method for electric double layer capacitive ion removal reported in 1966 has a problem of low ion removal capacity due to the limitations of the specific surface area of the electrode material and the pore structure. The battery-operated ion removal technology (BDI) proposed in 2012 is based on the bulk phase reaction of faraday electrochemical reaction, and has the advantage of high ion removal capacity. However, the electrode materials currently applied to such technologies have ion removal unity.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an electrode material which can simultaneously remove chloride ions and sodium ions in a water body.
The invention also provides a preparation method for preparing the electrode material.
The invention also provides application of the electrode material in water body ion removal technology.
The invention also provides a battery type ion removal system with the electrode material.
The invention also provides an electrochemical ion removal system with the battery type ion removal system.
The invention also provides the electrode material, a battery type ion removal system and application of the electrochemical ion removal system.
In a first aspect of the invention, an electrode material is provided, the electrode material is a bismuth-based material with a layered structure, and the bismuth-based material is MBi (sodium niobate) occupied by alkali metal and bismuth element together3O4X2M is an alkali metal, and X is halogen.
The electrode material provided by the embodiment of the invention has at least the following beneficial effects: the bismuth-based material is a layered structure material with the characteristic of electrochemical reversible phase change reaction, and has the anion and cation removal performance on water containing chloride ions and sodium ions based on the reversible phase change reaction due to the co-occupying characteristic of the layered structure, the contained bismuth element and the alkali metal element; the bismuth-based material is used in an electrochemical ion removal system, can effectively remove chloride ions and sodium ions in a water source, has high removal capacity, and can be recycled. Meanwhile, the preparation method of the bismuth-based material is simple, the raw materials are easy to obtain, the price is low, the implementation is easy, and the industrial large-scale production and application are facilitated. The electrode material has important application value for removing ions in sewage, seawater desalination, drinking water and the like.
For bismuth-based material NaBi3O4Cl2Taking the removal of chloride ions and sodium ions from water as an example, NaBi is realized3O4Cl2The conversion between/BiOCl/Bi is exemplified by the reaction mechanism shown in the chemical reaction formulas (1) to (2):
NaBi3O4Cl2+x·4H2O+x·9e-→x·(3Bi+Na++2Cl-+8OH-)+(1-x)·NaBi3O4Cl2 (1)
in some embodiments of the invention, M is at least one of lithium or sodium.
In some preferred embodiments of the invention, M is sodium.
In some embodiments of the invention, X is chlorine.
In some preferred embodiments of the invention, the MBi3O4X2Is NaBi3O4Cl2。
In some embodiments of the invention, the bismuth-based material has a space group I4/mmm.
In some embodiments of the invention, the bismuth-based material has an interlayer distance of
In a second aspect of the present invention, a method for preparing an electrode material is provided, which comprises the following steps: calcining the bismuth source and the alkali metal salt to obtain the bismuth-based material.
The preparation method of the electrode material provided by the embodiment of the invention has at least the following beneficial effects: the preparation method of the bismuth-based material is simple, the raw materials are easy to obtain, the price is low, the realization is easy, and the industrial large-scale production and application are convenient.
In some embodiments of the invention, the bismuth source comprises at least one of elemental bismuth, bismuth oxide, or a bismuth salt.
In some preferred embodiments of the invention, the bismuth salt comprises at least one of bismuth nitrate, bismuth carbonate, sodium bismuthate, or bismuth oxychloride.
It should be noted that, as can be seen from experiments, the experimental results obtained by respectively selecting bismuth nitrate, bismuth carbonate, sodium bismuthate or bismuth oxychloride are similar or nearly the same.
In some embodiments of the invention, the alkali metal salt comprises at least one of a sodium salt or a lithium salt.
In some preferred embodiments of the invention, the alkali metal salt comprises at least one of lithium fluoride, sodium fluoride, lithium chloride, sodium nitrate, lithium carbonate, or sodium carbonate.
It can be seen through experiments that lithium fluoride, sodium fluoride, lithium chloride, sodium nitrate, lithium carbonate or sodium carbonate are respectively selected, and the obtained experimental results are similar or nearly identical.
In some embodiments of the invention, the bismuth source and the sodium salt are in a mass ratio of 3:1 to 2.6: 0.58. In some embodiments of the invention, the calcination temperature is 600-1000 ℃.
In some preferred embodiments of the invention, the calcination temperature is 600-.
In some embodiments of the invention, the calcination time is from 3 to 10 days.
In some preferred embodiments of the invention, the calcination time is from 3 to 8 days.
In a third aspect of the invention, the application of the electrode material in a water body ion removal technology is provided.
In a fourth aspect of the invention, a battery-operated ion removal system is provided, comprising the above-described electrode material as a working electrode.
The battery type ion removal system provided by the embodiment of the invention at least has the following beneficial effects: due to the layered structure of the bismuth-based material and the co-occupying characteristics of the contained bismuth element and the alkali metal element, the bismuth-based material can perform reversible electrochemical redox reaction in a system containing chloride ions and sodium ions and can perform reversible electrochemical phase change reaction with the chloride ions and the sodium ions in the solution, so that the aim of removing the chloride ions and the sodium ions is fulfilled, the bismuth-based material has higher removal capacity and can be recycled. Meanwhile, the preparation method of the bismuth-based material is simple, the raw materials are easy to obtain, the price is low, the implementation is easy, and the industrial large-scale production and application are facilitated. The electrode material has important application value for removing ions in sewage, seawater desalination, drinking water and the like.
In some embodiments of the invention, a counter electrode is also included.
In some preferred embodiments of the present invention, the counter electrode comprises at least one of sodium titanium phosphate, sodium vanadium phosphate, sodium manganate, quinone-based polymer, or prussian blue-based material.
In some preferred embodiments of the invention, the counter electrode comprises NaTi2(PO4)3、Na2Mn5O10At least one of polyanthraquinone, polyquinone, iron-based Prussian blue or copper-based Prussian blue.
It should be noted that, as can be seen from experiments, NaTi is selected and used respectively2(PO4)3、Na2Mn5O10The experimental results obtained by the method are similar or almost the same.
In some embodiments of the invention, the mass ratio of the working electrode to the counter electrode is 7:4 to 2: 1.
It should be noted that the mass ratio of the working electrode and the counter electrode in the battery-type ion removal system is determined by the ion removal capacity values of the working electrode and the counter electrode themselves.
In some embodiments of the invention, the battery-operated ion removal system has an operating voltage of-2V to 2V.
In some preferred embodiments of the present invention, the battery-operated ion removal system has an operating voltage of 1V to 2V.
In some embodiments of the invention, the battery-operated ion removal system has an operating current density of 20 to 1000 mA/g.
In some preferred embodiments of the present invention, the battery-operated ion removal system has an operating current density of 60 to 100 mA/g.
In a fifth aspect of the invention, an electrochemical ion removal system is provided that includes the battery-operated ion removal system described above.
The electrochemical ion removal system provided by the embodiment of the invention has at least the following beneficial effects: due to the layered structure of the bismuth-based material and the co-occupying characteristics of the contained bismuth element and the alkali metal element, the bismuth-based material can perform reversible electrochemical redox reaction in a system containing chloride ions and sodium ions and can perform reversible electrochemical phase change reaction with the chloride ions and the sodium ions in the solution, so that the aim of removing the chloride ions and the sodium ions is fulfilled, the bismuth-based material has higher removal capacity and can be recycled. Meanwhile, the preparation method of the bismuth-based material is simple, the raw materials are easy to obtain, the price is low, the implementation is easy, and the industrial large-scale production and application are facilitated. The electrode material has important application value for removing ions in sewage, seawater desalination, drinking water and the like.
In some embodiments of the invention, the electrochemical ion removal system further comprises a cycling test device for electrochemical energy storage.
It should be understood that the structure of the electrochemical energy storage cycling test device and the connection manner of the electrochemical energy storage cycling test device and the electrochemical ion removal system are common in the market, and therefore, the technical personnel in the field can not influence the understanding of the actual protection scope of the application even if the description is not given.
Under the action of a test voltage of the circulating test equipment for electrochemical energy storage, a battery type ion removal system is used for removing target ions in a water body, Inductive Coupling Plasma (ICP) and Ion Chromatography (IC) tests are carried out on aqueous solutions before and after treatment of the electrochemical ion removal system to determine the ion removal capacity of the system, and then the quality setting of a working electrode and a counter electrode in the battery type ion removal system is adjusted according to the ion removal capacity of each electrode, so that chloride ions and sodium ions in the water body are removed to the maximum extent.
In a sixth aspect of the present invention, the electrode material, the battery-type ion removal system or the electrochemical ion removal system is provided for use in removing chloride ions and sodium ions in a water body.
Due to the layered structure and the co-occupying characteristic of the contained bismuth and sodium elements, the bismuth-based material can generate reversible electrochemical redox reaction in a system containing chloride ions and sodium ions and can generate reversible electrochemical phase change reaction with the chloride ions and the sodium ions in the solution, so that the aim of removing the chloride ions and the sodium ions is fulfilled, the bismuth-based material has higher removal capacity and can be recycled. Meanwhile, the preparation method of the bismuth-based material is simple, the raw materials are easy to obtain, the price is low, the implementation is easy, and the industrial large-scale production and application are facilitated. The electrode material has important application value for removing ions in sewage, seawater desalination, drinking water and the like.
In some embodiments of the invention, the body of water comprises at least one of river water, sea water, drinking water, or industrial waste water.
The invention has the following beneficial effects:
the bismuth-based material is a layered structure material with the characteristic of electrochemical reversible phase change reaction, and has the anion and cation removal performance on water containing chloride ions and sodium ions based on the reversible phase change reaction due to the co-occupying characteristic of the layered structure and the contained bismuth element and sodium element; the bismuth-based material is used in an electrochemical ion removal system, can effectively remove chloride ions and sodium ions in a water source, has high removal capacity and can be recycled;
the battery type ion removal system mainly comprises a working electrode made of bismuth-based materials for removing chloride ions and sodium ions and a counter electrode for removing the sodium ions, can be widely applied to the fields of seawater desalination, waste water and sewage chloride ion and sodium ion removal and the like, and can be recycled;
the electrochemical ion removal system comprises the battery type ion removal system, can be widely applied to the fields of seawater desalination, removal of chloride ions and sodium ions in sewage and wastewater and the like, and has wide application prospect.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a scanning electron microscope photograph of a bismuth-based material obtained in an example of the present invention, with a scale of 1 μm;
FIG. 2 is a schematic diagram of the operation of the battery-operated ion removal system in an embodiment of the present invention;
FIG. 3 is a diagram of the phase transition process in-situ X-ray test results of the bismuth-based material of the battery-type ion removal system in an embodiment of the present invention;
FIG. 4 is a graph showing the results of testing the cycle performance of the bismuth-based material in the battery-type ion removal system according to the embodiment of the present invention;
fig. 5 is a test chart of the capacity of the bismuth-based material of the battery-type ion removal system for removing chloride ions and sodium ions in seawater in the embodiment of the invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment discloses an electrode material, which is a bismuth-based material with a layered structure, wherein the bismuth-based material is NaBi occupying alkali metal sodium and bismuth together3O4Cl2The space group of the bismuth-based material is I4/mmm, and the interlayer distance is
In this embodiment, an electrode material is prepared, and the specific process is as follows: weighing 2.25g of bismuth oxide and 0.58g of sodium chloride, and manually grinding for 30min to obtain a uniform mixture; calcining the bismuth-based material at 600 ℃ for 6 days under the protective atmosphere to obtain the bismuth-based material, namely the electrode material.
The embodiment provides a battery-type ion removal system, which comprises a working electrode and a counter electrode, wherein the working electrode is made of bismuth-based material obtained by the operation, and the counter electrode is made of sodium titanium phosphate (NaTi)2(PO4)3)。
The embodiment provides an electrochemical ion removal system, which comprises a cycle test device for electrochemical energy storage and a battery-type ion removal system, is used for removing chloride ions and sodium ions in a water body, and comprises the following steps:
(1) under the action of a cycle test device for electrochemical energy storage, a battery type ion removal system is used for confirming the electrochemical ion removal conditions of the aqueous solution containing the chloride ions and the sodium ions, and the sum of the concentrations of the chloride ions and the sodium ions in the aqueous solution is 10000 ppm. The ion removal voltage is 2V, the adopted current density is 60mA/g, and the water solution adopts natural seawater;
(2) based on the step (1), selecting sodium titanium phosphate as a counter electrode, selecting 7g of a working electrode and 4g of the counter electrode through ion removal capacity calculation, assembling a battery type ion removal system, and removing anions and sodium ions in an aqueous solution; the operating conditions of the battery-operated ion removal system are: the voltage was 2V and the current density was 60 mA/g.
Fig. 2 is a schematic diagram of the operation of the obtained battery-type ion removal system.
According to the figure 2, in the process of charging the cycle test equipment for electrochemical energy storage, the bismuth-based material is subjected to oxidation reaction to remove chloride ions and sodium ions in the water body, and the counter electrode sodium titanium phosphate is subjected to reduction reaction to remove sodium ions in the water body; in the discharging process, the oxidized bismuth-based material is subjected to reduction reaction to release chloride ions and sodium ions in the bulk phase, and the reduced sodium titanium phosphate is subjected to oxidation reaction to release sodium ions in the bulk phase. The removal and extraction of chloride ions and sodium ions in the aqueous solution are realized by repeating the electrochemical cycle process.
Example 2
In this embodiment, an electrode material is prepared, and the specific process is as follows: weighing 2.6g of bismuth oxychloride and 0.58g of sodium chloride, and manually grinding for 30min to obtain a uniform mixture; calcining at 700 ℃ for 8d under the protective atmosphere to obtain the final bismuth-based material, namely the electrode material.
The embodiment provides a battery-type ion removal system, which comprises a working electrode and a counter electrode, wherein the working electrode is made of bismuth-based material obtained by the operation, and the counter electrode is made of sodium titanium phosphate (NaTi)2(PO4)3)。
The embodiment provides an electrochemical ion removal system, which comprises a cycle test device for electrochemical energy storage and a battery-type ion removal system, is used for removing chloride ions and sodium ions in a water body, and comprises the following steps:
(1) under the action of a cycle test device for electrochemical energy storage, the electrochemical ion removal conditions of the aqueous solution containing the chloride ions and the sodium ions are confirmed by a battery type ion removal system, and the sum of the concentrations of the chloride ions and the sodium ions in the aqueous solution is 20000 ppm. The ion removal voltage is 2V, the adopted current density is 60mA/g, and the water solution adopts natural seawater;
(2) based on the step (1), selecting sodium titanium phosphate as a counter electrode, selecting 7g of a working electrode and 4g of the counter electrode through ion removal capacity calculation, assembling a battery type ion removal system, and removing anions and sodium ions in an aqueous solution; the working conditions of the battery type ion removal system are as follows: the voltage was 2V and the current density was 60 mA/g.
Example 3
In this embodiment, an electrode material is prepared, and the specific process is as follows: weighing 3g of bismuth oxide and 1g of sodium chloride, and manually grinding for 30min to obtain a uniform mixture; calcining at 800 ℃ for 3d under a protective atmosphere to obtain the bismuth-based material, and obtaining the electrode material.
The embodiment provides a battery-type ion removal system, which comprises a working electrode and a counter electrode, wherein the working electrode is made of the bismuth-based material obtained through the operation, and the counter electrode is made of prussian blue.
The embodiment provides an electrochemical ion removal system, which comprises a cycle test device for electrochemical energy storage and a battery-type ion removal system, is used for removing chloride ions and sodium ions in a water body, and comprises the following steps:
(1) under the action of a cycle test device for electrochemical energy storage, the electrochemical ion removal conditions of the aqueous solution containing the chloride ions and the sodium ions are confirmed by a battery type ion removal system, and the sum of the concentrations of the chloride ions and the sodium ions in the aqueous solution is 30000 ppm. The ion removal voltage is 1V, the adopted current density is 100mA/g, and the water solution adopts natural seawater;
(2) selecting Prussian blue as a counter electrode based on the step (1), selecting 8g of working electrode and 4g of counter electrode through ion removal capacity calculation, assembling a battery type ion removal system, and removing chloride ions and sodium ions in an aqueous solution; the working conditions of the battery type ion removal system are as follows: the voltage was 1V and the current density was 100 mA/g.
Example 4
In this embodiment, an electrode material is prepared, and the specific process is as follows: weighing 2.6g of bismuth oxychloride and 0.58g of sodium chloride, and manually grinding for 30min to obtain a uniform mixture; calcining at 900 ℃ for 3d under the protective atmosphere to obtain the final bismuth-based material.
The embodiment provides a battery-type ion removal system, which comprises a working electrode and a counter electrode, wherein the working electrode is made of bismuth-based material obtained through the operation, and the counter electrode is made of sodium manganate.
The embodiment provides an electrochemical ion removal system, which comprises a cycle test device for electrochemical energy storage and a battery-type ion removal system, is used for removing chloride ions and sodium ions in a water body, and comprises the following steps:
(1) under the action of a cycle test device for electrochemical energy storage, the electrochemical ion removal conditions of the aqueous solution containing the chloride ions and the sodium ions are confirmed by a battery type ion removal system, and the sum of the concentrations of the chloride ions and the sodium ions in the aqueous solution is 50000 ppm. The ion removal voltage is 1V, the adopted current density is 100mA/g, and the water solution adopts natural seawater;
(2) based on the step (1), selecting sodium manganate as a counter electrode, selecting 8g of a working electrode and 4g of the counter electrode through ion removal capacity calculation, assembling a battery type ion removal system, and removing chloride ions and sodium ions in an aqueous solution; the working conditions of the battery type ion removal system are as follows: the voltage was 1V and the current density was 100 mA/g.
Test examples
This experimental example tested the electrode material and the battery-type ion removal system prepared in example 1. Wherein:
the microstructure of the electrode material-bismuth-based material prepared in example 1 was tested, and the test results are shown in fig. 1. Scanning electron microscope test conditions: the operating voltage was 5 kV.
The phase transition process of the electrode material-bismuth based material prepared in example 1 was tested by in-situ X-ray, and the test results are shown in fig. 3. X-ray test conditions: the test angle range is 10-60 deg., the step rate is 3 deg./min, the test voltage is discharged from 0V to-1V, and then charged to 0.3V.
The bismuth-based material for the battery-type ion removal system in example 1 was tested for cycle performance in a cycle test apparatus for electrochemical energy storage and current density in a voltage range employed, and the test results are shown in fig. 4. And (3) testing conditions are as follows: the current density is 60mA/g, and the voltage range is-1-0.3V.
The bismuth-based material of the battery-type ion removal system of example 1 was tested for anion and cation removal capacity, and the results are shown in fig. 5. The results were obtained from inductively coupled plasma and ion chromatography calculation tests.
As can be seen from FIG. 1, the bismuth-based material obtained by the preparation had a layered structure.
As can be seen from FIG. 3, NaBi is present during the charging process of the cycling test device for electrochemical energy storage3O4Cl2The phase diffraction peak of the/BiOCl is weakened along with the reduction process along with the strengthening of the oxidation process, and the diffraction peak of the Bi phase is weakened along with the reduction process along with the strengthening of the oxidation process. FIG. 3 shows the results for NaBi3O4Cl2The reversible phase separation reaction between the/BiOCl/Bi phases allows the simultaneous removal of chloride and sodium ions (equation 3).
Meanwhile, this experimental example tested the ion removal capacity of the electrochemical ion removal systems prepared in examples 1 to 4.
The test method comprises the following steps: inductively Coupled Plasma (ICP) and Ion Chromatography (IC) tests were performed on the aqueous solutions before and after treatment with the electrochemical ion removal systems of examples 1-4, respectively, to determine the ion removal capacity of the systems.
The electrochemical ion removal systems of examples 1-4 were tested for their total capacity for removing chloride and sodium ions from water, and the results are shown in table 1 below:
TABLE 1
| Examples | Total ion removal capacity (mg/g) |
| Example 1 | 100 |
| Example 2 | 80 |
| Example 3 | 70 |
| Example 4 | 80 |
As can be seen from table 1 and fig. 4 and 5, the battery-type ion removal system based on the bismuth-based material has good cycle stability and high removal capacity for chloride ions and sodium ions in water. The electrochemical ion removal systems of examples 1-4 are all able to better remove chloride and sodium ions from aqueous solutions.
In fig. 5, the removing effect tends to increase first and then decrease, and the mechanism is presumed to be that the electrode activation and ion channel establishment process exists at the early stage of the recycling process of the electrode material; along with the establishment of the ion transmission channel, the impedance is gradually reduced, the electrochemical reaction kinetics is enhanced, and the electrochemical performance is gradually improved.
The "protective atmosphere" in the above embodiments means under a nitrogen atmosphere or an inert gas atmosphere.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The electrode material is characterized in that the electrode material is a bismuth-based material with a layered structure, and the bismuth-based material is MBi (sodium niobate) occupied by alkali metal and bismuth element together3O4X2M is an alkali metal, and X is halogen.
2. The electrode material of claim 1, wherein M is at least one of lithium or sodium, and X is chlorine; preferably, the MBi3O4X2Is NaBi3O4Cl2(ii) a Preferably, the space group of the bismuth-based material is I4/mmm; preferably, the bismuth-based material has an interlayer distance of
3. The preparation method of the electrode material is characterized by comprising the following steps of: calcining the bismuth source and the alkali metal salt to obtain the bismuth-based material.
4. The method for preparing an electrode material according to claim 3, wherein the bismuth source comprises at least one of bismuth simple substance, bismuth oxide or bismuth salt; preferably, the bismuth salt comprises at least one of bismuth nitrate, bismuth carbonate, sodium bismuthate or bismuth oxychloride; preferably, the alkali metal salt comprises at least one of a sodium salt or a lithium salt; preferably, the alkali metal salt comprises at least one of lithium fluoride, sodium fluoride, lithium chloride, sodium nitrate, lithium carbonate or sodium carbonate.
5. The method as claimed in claim 4, wherein the calcination temperature is 600-1000 ℃ and the calcination time is 3-10 d.
6. A battery-type ion removal system comprising the electrode material according to any one of claims 1 to 2 as a working electrode or the electrode material produced by the production method according to any one of claims 3 to 5 as a working electrode.
7. The battery-operated ion removal system of claim 6, further comprising a counter electrode; preferably, the counter electrode comprises at least one of sodium titanium phosphate, sodium vanadium phosphate, sodium manganate, quinone polymer or prussian blue material; preferably, the counter electrode comprises NaTi2(PO4)3、Na2Mn5O10At least one of polyanthraquinone, polyquinone, iron-based Prussian blue or copper-based Prussian blue.
8. An electrochemical ion removal system comprising the battery-operated ion removal system of any one of claims 6-7.
9. Use of the electrode material according to any one of claims 1 to 2 or the electrode material prepared by the preparation method according to any one of claims 3 to 5 or the battery-operated ion removal system according to any one of claims 6 to 7 or the electrochemical ion removal system according to claim 8 for removing ions from a body of water.
10. Use according to claim 9, characterized in that: the ions are at least one of chloride ions or sodium ions.
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| CN106229498A (en) * | 2016-08-04 | 2016-12-14 | 武汉理工大学 | A kind of negative material being applicable to Water based metal ion battery and preparation method thereof |
| WO2018136130A1 (en) * | 2017-01-18 | 2018-07-26 | Wisconsin Alumni Research Foundation | Bismuth-based chloride-storage electrodes |
| CN113184964A (en) * | 2021-05-19 | 2021-07-30 | 同济大学 | Prussian blue analogue/titanium three-carbon composite material and preparation method and application thereof |
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| CN106229498A (en) * | 2016-08-04 | 2016-12-14 | 武汉理工大学 | A kind of negative material being applicable to Water based metal ion battery and preparation method thereof |
| WO2018136130A1 (en) * | 2017-01-18 | 2018-07-26 | Wisconsin Alumni Research Foundation | Bismuth-based chloride-storage electrodes |
| CN113184964A (en) * | 2021-05-19 | 2021-07-30 | 同济大学 | Prussian blue analogue/titanium three-carbon composite material and preparation method and application thereof |
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| WENFEI WEI ET AL.: "Electrochemical Driven Phase Segregation Enabled Dual-Ion Removal Battery Deionization Electrode", 《NANO LETTERS》 * |
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